JP5642151B2 - Polyolefin composition suitable for polyolefin masterbatch and injection molding - Google Patents

Polyolefin composition suitable for polyolefin masterbatch and injection molding Download PDF

Info

Publication number
JP5642151B2
JP5642151B2 JP2012501260A JP2012501260A JP5642151B2 JP 5642151 B2 JP5642151 B2 JP 5642151B2 JP 2012501260 A JP2012501260 A JP 2012501260A JP 2012501260 A JP2012501260 A JP 2012501260A JP 5642151 B2 JP5642151 B2 JP 5642151B2
Authority
JP
Japan
Prior art keywords
component
composition
weight
range
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2012501260A
Other languages
Japanese (ja)
Other versions
JP2012521461A (en
Inventor
チャラフォニ,マルコ
マッサリ,パオラ
ビオンディーニ,ジセラ
パンタレオーニ,ロベルト
ヴィレムス,サンダー
Original Assignee
サンアロマー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
Priority to EP09155831.2 priority Critical
Priority to EP09155831 priority
Priority to US21117409P priority
Priority to US61/211,174 priority
Application filed by サンアロマー株式会社 filed Critical サンアロマー株式会社
Priority to PCT/EP2010/053621 priority patent/WO2010108866A1/en
Publication of JP2012521461A publication Critical patent/JP2012521461A/en
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42244903&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JP5642151(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application granted granted Critical
Publication of JP5642151B2 publication Critical patent/JP5642151B2/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/06Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/04Thermoplastic elastomer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00Masterbatches

Description

  The present invention relates to a polyolefin masterbatch that can be used to produce a polyolefin composition suitable for injection molding into relatively large articles. More particularly, the polyolefin composition can be injection molded to large objects that exhibit improved surface properties, particularly with respect to tiger striping and gels.

  Polypropylene and thermoplastic polyolefins have gained wide commercial acceptance due to their remarkable cost performance characteristics. For example, these polymers are used in molded coloring applications because of their good weather resistance.

  Polypropylene and thermoplastic polyolefins are generally injection molded into a variety of desired articles. Injection molding techniques for obtaining relatively large parts such as automotive bumpers and instrument panels present particularly difficult challenges such as cold flow, tiger stripes and gels. “Cold flow” occurs when the molten polymer that is injection molded into the mold cools and begins to solidify before the mold is completely filled with polymer. This is due to improper mold filling properties of the molten polymer when the molten polymer is injected into a mold to form the desired shape. “Gel” refers to a speckled appearance on the surface of a final formed article that occurs due to a relatively poor dispersion of one or more polymer components. Such a tiger stripe pattern or gel has the effect of deteriorating the surface appearance of the final formed article.

Various proposals have been made in the art to improve the physical properties of injection molded articles.
According to WO 2004/087805, a particularly good balance of melt fluidity, mechanical properties and surface properties is added to the polyolefin matrix, particularly referring to the reduction of tiger stripes, with the following masterbatch composition: Is achieved. This master batch composition has a melt flow rate (MFR) measured according to ISO 1133 (230 ° C./2.16 kg) of 0.1 to 10 g / 10 minutes, preferably in the range of 0.1 to 5 g / 10 minutes. Showing flexural modulus values up to 930 MPa (in% by weight):
A) Fraction A I showing melt flow rate MFR I of 0.1-10 g / 10 min from 25% to 75% and Fraction A II showing melt flow rate MFR II of 100 g / 10 min or less from 75% to 25% % Of crystalline polypropylene component containing 50% to 90%, where the MFR I / MFR II ratio is 5 to 60; and B) from ethylene and at least one C 3 -C 10 -α-olefin A copolymer component of 10% to 50%, wherein the copolymer contains 15 to 50% ethylene;
The intrinsic viscosity [η] of the xylene-soluble fraction at room temperature of the masterbatch composition is 3.5 dl / g.

  An important aspect associated with the use of the masterbatch composition is dispersion in the polyolefin matrix, which, if not optimal, can result in a significant number of gels in the final formed article.

  Accordingly, the object of the present invention is particularly suitable for being dispersed in a polyolefin blend that provides a final formed article having an excellent surface appearance by substantially reducing the amount of gel and reducing the striped pattern. The object is to provide a masterbatch composition with valuable physical and mechanical properties.

Therefore, the present invention
A propylene homopolymer or a copolymer of propylene and ethylene or C 4 -C 10 α-olefins, with a MFR A according to ISO 1133 (230 ° C./2.16 kg) in the range of 15-70 g / 10 min. A propylene-ethylene copolymer containing 70 to 90% by weight of component A; and -25 to 45% by weight of ethylene-derived units and having an intrinsic viscosity [η] of the xylene-soluble fraction at room temperature of 5 to 9 dl / g. 10-30% by weight of certain component B
A masterbatch composition having a total MFR higher than 4 g / 10 min and a flexural modulus value measured in accordance with ISO method 178 of 950 to 2000 MPa. It is to be.

All percentages are relative to the sum of components (A) and (B).
Preferably, the amount of component A) is in the range of 74 to 86% by weight, while component B) is preferably present in an amount in the range of 14 to 26% by weight, the ethylene derived unit content being Preferably, it is 30 to 42% by weight. More preferably, the intrinsic viscosity [η] of component B) is 6.5 to 8 dl / g.

Preferably, the MFR A of component (A) is in the range of 20-60 g / 10 min, while the MFR of the total composition is preferably 4-15 g / 10 min, more preferably 6-10 g / min. It is. In a preferred embodiment, the flexural modulus of the total composition measured according to ISO method 178 is in the range of 1000-1700 MPa.

  Furthermore, a preferred feature of the masterbatch composition of the present invention is that P.I. I. (Polydispersity index) is greater than 5, preferably in the range of 5-10, and more preferably in the range of 5.5-9. The polydispersity index means the width of the molecular weight distribution (MWD) of the component (A) measured according to the rheological method described in the characterization section below. A PI value higher than 5 is an indication of component (A) showing a broad molecular weight distribution (MWD). Such broad MWD is generally different for polymers with wide MWD, either by using catalyst components that can themselves produce broad MWD polymers or by obtaining polymer fractions with different molecular weights. It can be obtained by adopting a specific process such as polymerization in the lower multi-step. In a preferred embodiment of the invention, the propylene homopolymer or propylene copolymer can contain two or more fractions having different MFRs.

Component (A) contains ethylene and / or C 4 -C 10 derived units in an amount in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the amount of copolymer A). Can be contained.
The composition of the present invention shows an optimal balance between rigidity and impact strength, and has an Izod impact resistance at 23 ° C. of 5 to 100 KJ / m 2 , preferably 5 to 60 KJ / m 2 , more preferably 8 This is proved by showing a value of ˜50 KJ / m 2 . The Izod impact resistance value at −20 ° C. is 3 to 20 KJ / m 2 , preferably 3.5 to 10 KJ / m 2 .

  The masterbatch composition of the present invention can be produced by continuous polymerization comprising at least two continuous steps, wherein components A) and B) are formed in the previous step, operating in each step (except for the first step). In a separate continuous process in the presence of the polymer and catalyst used in the previous stroke. In particular, component A) may require one or more continuous steps.

  When produced in one step, the molecular weight distribution of component A) is unimodal. When manufacturing in two or more steps, the molecular weight distribution of component A) can be unimodal if the same polymerization conditions are maintained in all polymerization steps, or polymerize during various polymerization stages. By varying the conditions, for example, by varying the amount of molecular weight modifier, it can be a multimodal molecular weight distribution.

  The polymerization, which can be continuous or batch, is carried out according to known techniques (including mixed-gas techniques) operating either in the liquid phase or in the gas phase. Liquid phase polymerization can be slurry polymerization performed in the presence of an inert solvent or bulk polymerization in which the liquid medium is composed of liquid monomers.

  The polymerization is preferably carried out in the presence of the well-known stereospecific Ziegler-Natta catalyst. Preferably, the catalyst system used to prepare the polymer composition of the present invention comprises (A) a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron donor compound (both halogen And (B) an organoaluminum compound such as an alkylaluminum compound as a cocatalyst. An external electron donor compound may optionally be added as another component (C).

  The catalyst typically used in the process of the present invention can produce polypropylene with an isotactic index greater than 90%, preferably greater than 95%. Suitable catalyst systems are described in European patents EP 45777, EP 361494, EP 728769, EP 1272533 and in international patent application WO 00/63261.

  The solid catalyst component used for the catalyst is a compound selected from the group consisting of ethers, ketones, and esters of monocarboxylic acids and dicarboxylic acids as electron donors (internal donors).

  Particularly suitable electron donor compounds are phthalates such as diisobutyl phthalate, dioctyl phthalate, diphenyl phthalate and benzyl butyl phthalate.

  Another suitable electron donor compound is a succinic acid ester, preferably the following formula (I):

In which the R 1 and R 2 groups are equal or different and are C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups, optionally heterogeneous. The R 3 to R 6 groups can be equal or different and are hydrogen or a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, R 3 to R 6 groups that can contain heteroatoms and are bonded to the same carbon atom can be bonded together to form a ring; provided that when R 3 to R 5 groups are simultaneously hydrogen, R 6 is Primary, branched, secondary or tertiary alkyl groups, cycloalkyl, aryl, arylalkyl or alkylaryl groups These are linear alkyl groups having from 3 to 20 carbon atoms, or having at least 4 carbon atoms, optionally containing heteroatoms.) Selected from succinates Is done.

The catalyst component is produced by various methods.
In a preferred method, the solid catalyst component is a titanium compound of formula Ti (OR) ny X y , where n is the valence of titanium and y is a number between 1 and n, preferably TiCl 4 and the formula MgCl 2 · pROH (wherein p is a number between 0.1 and 6, preferably 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms. In the reaction with magnesium chloride derived from the adduct. The adduct is a sphere obtained by mixing alcohol and magnesium chloride by mixing them under the stirring conditions at the melting point of the adduct (100 to 130 ° C.) in the presence of an inert hydrocarbon that cannot be mixed with the adduct. Can be manufactured properly. The resulting emulsion is then quenched, thereby leading to the solidification of the adduct in the form of spherical particles. Examples of spherical adducts produced by this procedure are described in US Pat. Nos. 4,399,054 and 4,469,648. The adduct thus obtained can be reacted directly with the Ti compound, or the adduct is preliminarily obtained so as to obtain an adduct whose molar number of alcohol is generally less than 3, preferably 0.1 to 2.5. It can be subjected to a temperature-controlled (80 to 130 ° C.) dealcoholization treatment. The reaction with the Ti compound involves suspending the adduct (with or without alcohol) in cold TiCl 4 (approximately 0 ° C.), heating the resulting mixture to 80-130 ° C., and bringing this temperature to 0 ° C. It can be carried out by maintaining for 5 to 2 hours. The treatment with TiCl 4 can be performed one or more times. An internal donor can be added during the treatment with TiCl 4 and the treatment with the electron donor can be repeated one or more times. Generally, the internal electron donor, with respect to MgCl 2, 0.01 to 1, preferably used in a molar ratio of 0.05 to 0.5. The production of spherical catalyst components is described, for example, in European Patent Application EP-A-395083 and International Patent Application WO 98/44001. The solid catalyst component obtained by the method, typically, 20 to 500 m 2 / g, preferably, (by B.E.T. method) surface area of 50 to 400 m 2 / g, greater than 0.2 cm 3 / g, Preferably, the total porosity (by BET method) of 0.2 to 0.6 cm 3 / g is shown. The porosity (Hg method) with pores with radii up to 10.000 mm is typically in the range of 0.3 to 1.5 cm 3 / g, preferably 0.45 to 1 cm 3 / g.

  In the solid catalyst component, the titanium compound represented as Ti is typically present in an amount of 0.5 to 10% by weight. The amount of electron donor compound that remains fixed to the solid catalyst component is typically from 5 to 20 mol% with respect to the magnesium dihalide.

  The above reaction results in the formation of an active form of magnesium halide. Other reactions are known in the literature, starting from magnesium compounds other than halides, such as magnesium carboxylate, leading to the formation of active forms of magnesium halides.

The organoaluminum compound is preferably an alkyl- selected from trialkylaluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. Al. Mixtures of trialkylaluminums and alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt 2 Cl and Al 2 Et 3 Cl 3 may be used.

Al-alkyl compounds are typically used in amounts such that the Al / Ti ratio is 1-1000.
Suitable external electron donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and the like, in particular 2,2,6,6- Tetramethylpiperidine, ketones, 1,3-diethers and the like. Another type of suitable external electron donor compound is the formula R a 5 R b 6 Si (OR 7 ) c , wherein a and b are integers from 0 to 2, and c is an integer from 1 to 3. Yes, the total (a + b + c) is 4, and R 5 , R 6 , and R 7 are alkyl, cycloalkyl, or aryl groups having 1-18 carbon atoms, optionally containing heteroatoms Good) silicon compounds. Particularly preferred are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane and 1,1,1-trifluoropropyl-2-ethylpiperidinyldimethoxysilane and 1,1,1-trifluoro Propyl-methyl-dimethoxysilane. The external electron donor compound is used in an amount that gives a molar ratio between the organoaluminum compound and the electron donor compound of 0.1 to 500.

  As mentioned above, the polymerization process can be carried out in the gas phase and / or in the liquid phase. As an example, the polymerization of propylene polymer (A) in the liquid phase uses liquid propylene as a diluent, while the copolymerization step to obtain the propylene copolymer fraction (B) involves partial degassing of monomers. It can be carried out in the gas phase without any intermediate steps. Alternatively, all continuous polymerization steps can be performed in the gas phase. The reaction time, reaction temperature and reaction pressure of the polymerization stage are not critical, but the temperature for the production of fractions (A) and (B), which can be the same or different, is usually between 50 ° C. and 120 ° C. is there. The polymerization pressure is preferably in the range of 0.5 to 12 MPa when the polymerization is carried out in the gas phase. The catalyst system can be pre-contacted (pre-polymerized) with a small amount of olefins. The molecular weight of the propylene polymer composition is adjusted by using known regulators such as hydrogen.

  Preferably, component A) is obtained by a polymerization process carried out in the liquid phase as described in European Patent Application No. EO1901922, or as described in WO 02/05192. Manufactured by a gas phase polymerization process.

  Although the order of production of components A) and B) is not critical, preferably component B) is produced after the production of the subsequent component A) fluidized according to the preferred embodiment, and the propylene polymer (A) Is produced by a gas phase polymerization process carried out in at least two interconnected polymerization zones. Such a polymerization process is described in European patent EP 782587.

  This process is carried out in the first and second interconnected polymerization zones, and propylene and ethylene or propylene and α-olefins are supplied to the polymerization zone in the presence of a catalyst system, and the produced polymer is discharged from the zone. To do. Growing polymer particles flow in the first polymerization region (rising tube) under rapid fluidization conditions, leave the first polymerization region, enter the second polymerization region (downcomer), and gravity Under the action, the polymer particles flow in a concentrated form, leave the second polymerization zone and are reintroduced into the first polymerization zone, thus establishing a polymer circulation between the two polymerization zones.

  Generally, the conditions for rapid flow in the first polymerization zone are established by feeding a monomer gas mixture below the reintroduction point of the growing polymer into the first polymerization zone. The speed of the moving gas into the first polymerization zone is faster than the moving speed under the operating conditions, typically 2-15 m / sec. In the second polymerization zone, where the polymer flows in a concentrated form under the action of gravity, a high value of solid density is achieved, which approaches the bulk density of the polymer and thus, along the flow direction, A favorable benefit is obtained, as a result of which it is possible to reintroduce the polymer into the first reaction zone without the aid of mechanical means. In this way, a “loop” circulation is established, which is determined by the pressure balance between the two polymerization zones and by the head loss introduced into the system. Optionally, one or more inert gases, such as nitrogen or aliphatic hydrocarbons, in an amount such that the total partial pressure of the inert gas is preferably 5-80% of the total pressure of the gas. maintain. For example, operating parameters such as temperature are, for example, between 50 ° C. and 120 ° C., as is customary in gas phase olefin polymerization processes. The pressure is 0.5 to 10 MPa, preferably 1.5 to 6 MPa. Preferably, various catalyst components are fed to the first polymerization zone at any point in the first polymerization zone. However, they can also be supplied at any point in the second polymerization zone. Molecular weight modifiers known in the art can be used, in particular, to regulate the molecular weight of the polymer growing hydrogen.

  In a second stage of the particularly preferred polymerization process, the propylene / ethylene copolymer (B) is produced in a conventional fluidized bed gas phase reactor in the presence of the polymeric material and catalyst system resulting from the previous polymerization step. The resulting polymerization mixture is discharged from the downcomer to a gas-solid separator and subsequently fed to a fluidized bed gas phase reactor operating under conventional temperature and pressure conditions.

  The propylene polymer composition of the present invention uses the same catalyst as described above and operates under substantially the same polymerization conditions to produce the copolymers (A) and (B) separately, followed by the molten state Both of these copolymers can also be obtained by mechanical blending using conventional mixing equipment such as a twin screw extruder.

The masterbatch composition of the present invention may also contain additives conventionally used in the art such as antioxidants, light stabilizers, heat stabilizers, colorants and fillers.
As noted above, the masterbatch composition of the present invention is advantageously formulated with additional polyolefins, particularly propylene polymers such as propylene homopolymers, random copolymers and thermoplastic elastomer polyolefin compositions. be able to.

  Accordingly, another aspect of the present invention relates to a thermoplastic polyolefin composition suitable for injection molding that contains a masterbatch composition as defined above. Preferably, the thermoplastic polyolefin composition comprises up to 30 wt%, preferably 8-25 wt%, more preferably 10-20 wt% of the masterbatch composition of the present invention.

Examples of polyolefins to which the masterbatch is added (ie polyolefins other than present in the masterbatch) are the following polymers. That is,
1) crystalline propylene homopolymers, in particular isotactic homopolymers or predominantly isotactic homopolymers;
2) Crystalline propylene copolymers with ethylene and / or C 4 -C 10 α-olefins, wherein the total comonomer content ranges from 0.05% to 20% by weight relative to the weight of the copolymer. And preferred α-olefins are 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene;
3) Crystalline ethylene homopolymers and crystalline copolymers of ethylene with propylene and / or C 4 -C 10 α-olefins such as HDPE;
4) Elastomer copolymers of ethylene and propylene and / or C 4 -C 10 α-olefins, such as butadiene, 1,4-hexadiene, 1,5-hexadiene and ethylidene-1-norbornene in some cases May contain small amounts of dienes, where the diene content is typically 1 to 10% by weight;
5) A thermoplastic elastomer composition comprising an elastomer portion comprising one or more propylene homopolymers and / or copolymers of 2) above and one or more copolymers of 4) above, typically in the molten state Thermoplastic elastomer compositions prepared according to known methods by mixing the components or by continuous polymerization, typically polymers containing said elastomer part in an amount of 5 to 80% by weight.

  The polyolefin composition is prepared by mixing the masterbatch composition and additional polyolefin (s) together, extruding the resulting mixture, and pelletizing the resulting composition using known techniques and equipment. can do.

The polyolefin composition can also contain conventional additives such as inorganic fillers, colorants and stabilizers. Inorganic fillers that can be included in the composition include talc, CaCO 3 , silicon such as wollastonite (CaSiO 3 ), clay, diatomaceous earth, titanium oxide and zeolite. Typically, inorganic fillers are in particulate form with an average diameter in the range of 0.1-5 μm.

The present invention also provides final articles such as bumpers and fascias made from the polyolefin composition.
The practice and advantages of the present invention are illustrated in the following examples. These examples are for illustration only and are not intended to limit the patentable scope of the invention in any way.

The following analytical methods are used to characterize the polymer composition.
Melting flow rate : ASTM-D1238, condition L.
Intrinsic viscosity [η] : determined in tetrahydronaphthalene at 135 ° C.
Ethylene content : R. Spectroscopy.
Flexural modulus : ISO178
Yield point strength : ISO 527
Strength at break : ISO 527
Elongation at break and elongation at yield : ISO 527
Notched Izod impact test : ISO180 / 1A
Polydispersity index (PI) :
It is determined at a temperature of 200 ° C. by using a parallel plate rheometer model RMS-800 available from RHEOMETRICS (USA), which operates to increase the frequency from 0.1 rad / sec to 100 rad / sec. The polydispersity index value is given by the formula: I. = 10 5 / Gc (where Gc is a crossover modulus defined as a value (expressed in Pa) when G ′ = G ″ (G ′ is a storage modulus and G ″ is a loss modulus)) Derived from the crossover modulus.
2.5 g of polymer and 250 cm 3 of xylene are introduced into a glass flask equipped with a xylene soluble fraction refrigerator and a magnetic stirrer. The temperature is raised to the boiling point of the solvent within 30 minutes. The clear solution thus obtained is then maintained under reflux and stirred for a further 30 minutes. The sealed flask is then maintained in an ice-water bath for 30 minutes and in a water bath at a constant temperature of 25 ° C. for an additional 30 minutes. The solid thus formed is filtered through a quick filter paper. 100 cm 3 of the filtrate is poured into a pre-weighed aluminum container that is heated on a heating plate under a stream of nitrogen and the solvent is removed by evaporation. The container is then maintained in an oven at 80 ° C. under vacuum until a constant weight is obtained. The percentage of polymer that dissolves in xylene at room temperature is then calculated.
The tiger stripe pattern ratio is determined by a child that evaluates the tiger stripe pattern ratio calculated after the molten polymer is injected into the center of the hollow spiral mold. This ratio is expressed by the distance between the injection point and the first striped pattern visible on the coagulated polymer, divided by the total length of the coagulated polymer helix. The evaluation is performed using a Krauss-Maffei KM250 / 1000C2 machine that operates under the following conditions. The condition is
● Melting temperature: 230 ℃
● Molding temperature: 50 ℃
● Injection pressure: 180 bar ● Average injection speed: 10 mm / sec ● Switching pressure: 28 bar ● Switching pressure time: 15 sec ● Cooling time: 20 sec ● Spiral thickness: 2.0 mm
● Spiral width: 50. mm
● Clamping force: 2500kN
It is.

  The effect of the composition of the present invention to reduce the tiger stripe pattern is evaluated by determining its influence in the standard formula. The standard formula is obtained by mixing with a certain amount of the masterbatch composition of the present invention and the other components shown in Table 1. These formulations were prepared in an internal mixer.

The ethylene copolymer contains one or more C 3 -C 10 α-olefins as a comonomer and exhibits an intrinsic viscosity η of 1.85 dl / g.
Gel evaluation:
Quantitative evaluation by observing the appearance of the bumper and counting the number of gels on the plaque.

Example 1
Preparation of solid catalyst component 250 mL of TiCl 4 was introduced at 0 ° C. into a nitrogen purged 500 mL four neck round bottom flask. While stirring, 10.0 g of microspheres MgCl 2 · 2.8C 2 H 5 OH (prepared according to the method described in Example 2 of US Pat. No. 4,399,054, but instead of 10,000 rpm And 7.4 mmol of diethyl 2,3-diisopropyl succinate were added. The temperature was raised to 100 ° C. and maintained for 120 minutes. Stirring was then stopped, the solid product was allowed to settle, and the supernatant was removed by siphon. Then 250 mL of fresh TiCl 4 was added. Next, the obtained mixture was reacted at 120 ° C. for 60 minutes, and the supernatant was removed by siphon. The resulting solid was washed 6 times using anhydrous hexane at 60 ° C. (6 × 100 mL).

Prior to introduction into the catalyst system and prepolymerization polymerization reactor, the solid catalyst component obtained above was mixed with aluminum triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS) at 12 ° C. for 24 minutes and TEAL vs. solid catalyst component. Contact is made in such an amount that the weight ratio is equal to 11 and the TEAL / DCPMS weight ratio is equal to 4.4.

The catalyst system is then subjected to prepolymerization by being kept suspended in liquid propylene for about 5 minutes at 20 ° C. before being introduced into the first polymerization reactor.
A composition was prepared by continuously performing in a series of three reactors equipped with a device for transporting the polymerization product from one reactor to the reactor immediately below. Component (A) was prepared by operating under the same conditions in the first and second reactor bulk loop reactors, while component (B) was prepared in a third conventional fluidized bed gas phase reactor. In a liquid monomer polymerization reactor, the propylene homopolymer (component (A)) is added in a continuous and constant flow to the propylene stream in accordance with the conditions reported in Table 1, catalyst components, aluminum triethyl (TEAL), and external It was produced by separately supplying dicyclopentyldimethoxysilane and hydrogen (used as molecular weight modifier) as donors.

  After the polypropylene homopolymer produced in the first reactor is discharged into a continuous flow and purged of unreacted monomers, the polypropylene homopolymer in the continuous flow is placed in a gas phase polymerization reactor with a constant flow of gas. Introduced with phase hydrogen, ethylene and propylene to produce a propylene / ethylene copolymer (component (B)).

  The polymer particles present in the final reactor were subjected to a steam treatment to remove reactive monomers and volatiles and then dried. The composition thus obtained is subjected to mechanical characterization and the results are reported in Table 1. Further, in order to evaluate the effectiveness of the corrected tiger stripe pattern, the composition was subjected to the test under the conditions shown in the item of characterization. The results are reported in Table 2.

(Example 2)
The same catalyst as described in Example 1 was used. The composition was made in succession in a series of four reactors equipped with equipment to transfer the product from one reactor to the reactor immediately below. Component (A) was prepared in first and second reactor bulk loop reactors operating in the same polymerization reaction conditions and in a first fluidized bed gas phase reactor. Component (B) was prepared in a second fluidized bed gas phase reactor. In a liquid monomer loop polymerization reactor, in a continuous and constant stream, the catalyst components in the propylene stream, aluminum triethyl (TEAL), and dicyclopentyldimethoxysilane as an external donor, hydrogen (used as molecular weight regulator), Propylene homopolymer (component (A)) was prepared by feeding separately according to the conditions reported in Table 1.

  The propylene homopolymer produced in the bulk loop reactor is discharged into a continuous stream and introduced into the first gas phase polymerization reactor in a continuous stream with a certain amount of hydrogen and propylene in the gas phase, with different molecular weights. Another fraction of a propylene homopolymer having was produced. After the propylene homopolymer produced in the first gas phase polymerization reactor is discharged into the continuous flow and the unreacted monomer is purged, the propylene homopolymer in the continuous flow is flown into the second gas phase polymerization reactor at a constant flow. Together with hydrogen, vapor phase ethylene and propylene to produce a propylene / ethylene copolymer (component (B)).

  The polymer particles present in the final reactor were subjected to a steam treatment to remove reactive monomers and volatiles and then dried. The composition thus obtained is subjected to mechanical characterization and the results are reported in Table 1. Further, in order to evaluate the effectiveness of the corrected tiger stripe pattern, the composition was subjected to the test under the conditions shown in the item of characterization. The results are reported in Table 2.

Claims (8)

  1. A propylene homopolymer or a copolymer of propylene and ethylene or C 4 -C 10 α-olefins, with a MFR A according to ISO 1133 (230 ° C./2.16 kg) in the range of 15 to 70 g / 10 min. Propylene-ethylene containing 70 to 90% by weight of certain component (A); and -25 to 45% by weight of ethylene-derived units and having an intrinsic viscosity [η] of the xylene-soluble fraction at room temperature of 5 to 9 dl / g 10-30% by weight of component (B) which is a copolymer
    A master batch composition having a total MFR higher than 4 g / 10 min and a flexural modulus value measured according to ISO method 178 of 950 to 2000 MPa.
  2.   The amount of the component (A) is in the range of 74 to 86% by weight, the amount of the component (B) is 14 to 26% by weight, and the content of the ethylene derived unit in the component (B) is 30 to 42% by weight. The masterbatch composition according to claim 1.
  3.   The masterbatch composition of Claim 1 whose intrinsic viscosity value [(eta)] of a component (B) is 6.5-8 dl / g.
  4. The masterbatch composition according to claim 1, wherein the MFR A of component (A) is in the range of 20-60 g / 10 min and the MFR of the total composition is in the range of 4-15 g / 10 min.
  5.   The masterbatch composition according to claim 1, wherein the flexural modulus measured according to ISO method 178 is in the range of 1000 to 1700 MPa.
  6.   P. of component (A) I. The master batch composition according to claim 1, wherein (polydispersity index) is in the range of 5-10.
  7. The manufacturing method of a thermoplastic polyolefin composition including the process of mixing the masterbatch composition in any one of Claims 1-6, and polyolefins other than this .
  8. A step of mixing the masterbatch composition according to any one of claims 1 to 6 with other polyolefins to obtain a thermoplastic polyolefin composition; and
    The manufacturing method of the articles | goods including the process of shape | molding the said thermoplastic polyolefin composition .
JP2012501260A 2009-03-23 2010-03-19 Polyolefin composition suitable for polyolefin masterbatch and injection molding Active JP5642151B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP09155831.2 2009-03-23
EP09155831 2009-03-23
US21117409P true 2009-03-27 2009-03-27
US61/211,174 2009-03-27
PCT/EP2010/053621 WO2010108866A1 (en) 2009-03-23 2010-03-19 Polyolefin masterbatch and composition suitable for injection molding

Publications (2)

Publication Number Publication Date
JP2012521461A JP2012521461A (en) 2012-09-13
JP5642151B2 true JP5642151B2 (en) 2014-12-17

Family

ID=42244903

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2012501260A Active JP5642151B2 (en) 2009-03-23 2010-03-19 Polyolefin composition suitable for polyolefin masterbatch and injection molding

Country Status (8)

Country Link
US (2) US9309394B2 (en)
EP (1) EP2411464B1 (en)
JP (1) JP5642151B2 (en)
KR (1) KR101693062B1 (en)
CN (1) CN102361927B (en)
BR (1) BRPI1013551A2 (en)
RU (1) RU2531352C2 (en)
WO (1) WO2010108866A1 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010149705A1 (en) * 2009-06-26 2010-12-29 Basell Poliolefine Italia S.R.L. Polyolefin compositions
CN102985478B (en) * 2010-07-23 2015-04-29 巴塞尔聚烯烃意大利有限责任公司 Propylene polymer compositions
ES2692860T3 (en) 2010-12-20 2018-12-05 Braskem America, Inc. Improved-looking propylene-based compositions and excellent mold fluidity
JP5841245B2 (en) 2011-05-20 2016-01-13 アイエムフラックス インコーポレイテッド Method for injection molding at low pressure and at substantially constant pressure
BR112013029694A2 (en) 2011-05-20 2017-01-17 Procter & Gamble alternative pressure control for a low constant pressure injection molding apparatus
CA2913161C (en) 2011-05-20 2017-11-14 Gene Michael Altonen Method and apparatus for substantially constant pressure injection molding of thinwall parts
CN103842148B (en) * 2011-05-20 2017-04-05 艾姆弗勒克斯有限公司 The method being molded under the low pressure of substantial constant
AU2012258945B2 (en) 2011-05-20 2016-02-11 iMFLUX Inc. Non-naturally balanced feed system for an injection molding apparatus
CA2836783C (en) 2011-05-20 2017-02-21 The Procter & Gamble Company Apparatus and method for injection molding at low constant pressure
EP2729528B1 (en) * 2011-07-07 2015-04-29 Basell Poliolefine Italia S.r.l. Polypropylene composition
WO2013126723A1 (en) 2012-02-24 2013-08-29 The Procter & Gamble Company Injection mold having a simplified cooling system
US20130295219A1 (en) 2012-05-02 2013-11-07 Ralph Edwin Neufarth Injection Mold Having a Simplified Evaporative Cooling System or a Simplified Cooling System with Exotic Cooling Fluids
EP2669329A1 (en) 2012-06-01 2013-12-04 Basell Poliolefine Italia S.r.l. Mineral-filled polypropylene composition for foaming
US9604398B2 (en) 2012-11-08 2017-03-28 Imflux Inc Injection mold with fail safe pressure mechanism
CN105073379B (en) 2012-11-21 2017-04-26 艾姆弗勒克斯有限公司 Reduced size runner for an injection mold system
EP2738214B1 (en) 2012-11-29 2015-05-06 Borealis AG Tiger stripe modifer
EP2738215B1 (en) 2012-11-29 2015-05-27 Borealis AG Tiger stripe modifier
KR101770487B1 (en) 2012-11-30 2017-08-22 보르쥬 컴파운딩 상하이 캄파니 리미티드 Pp compounds with alleviated or eliminated tiger stripe and retained excellent mechanical properties
EP2787034A1 (en) * 2013-04-05 2014-10-08 Borealis AG High stiffness polypropylene compositions
US10047218B2 (en) 2013-12-20 2018-08-14 Saudi Basic Industries Corporation Polyolefin composition
EP3159377A1 (en) 2015-10-23 2017-04-26 Borealis AG Heterophasic composition
BR112019000684A2 (en) * 2016-07-18 2019-04-24 Equistar Chem Lp compatibilizer polyolefin composition for the formulation to enhance balance in rigidity and impact
JP2018100335A (en) 2016-12-20 2018-06-28 サンアロマー株式会社 Master batch composition

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1096661B (en) 1978-06-13 1985-08-26 Montedison Spa Process for the preparation of products in spheroidal form solids at room temperature
IT1098272B (en) 1978-08-22 1985-09-07 Montedison Spa Components of catalysts and catalysts for the polymerization of alpha-olefins
IT1209255B (en) 1980-08-13 1989-07-16 Montedison Spa Catalysts for the polymerization of olefins.
JPS6031868B2 (en) * 1981-12-25 1985-07-24 Ube Kosan Kk
IT1227258B (en) 1988-09-30 1991-03-28 Himont Inc Components and catalysts for the polymerization of olefins
IT1230134B (en) 1989-04-28 1991-10-14 Himont Inc Components and catalysts for the polymerization of olefins.
IL117114A (en) 1995-02-21 2000-02-17 Montell North America Inc Components and catalysts for the polymerization ofolefins
IT1275573B (en) 1995-07-20 1997-08-07 Spherilene Spa Process and apparatus for the pomimerizzazione in the gas phase of alpha-olefins
AUPO591797A0 (en) 1997-03-27 1997-04-24 Commonwealth Scientific And Industrial Research Organisation High avidity polyvalent and polyspecific reagents
BR9908379B1 (en) * 1998-12-24 2008-11-18 bottle caps and process for producing bottle caps.
BR0006095B1 (en) 1999-04-15 2013-06-18 solid catalytic component and catalyst for olefin polymerization as well as process for (co) polymerization of olefins.
US6586531B2 (en) * 2000-10-04 2003-07-01 Basell Poliolefine Italia S.P.A. Polyolefin masterbatch and composition suitable for injection molding
PL355609A1 (en) 2000-10-13 2004-05-04 Basell Poliolefine Italia S.P.A. Catalyst components for the polymerization of olefines
BR0108588B1 (en) 2000-12-22 2011-04-05 polyolefinic sheets for thermoforming.
CA2478513A1 (en) * 2002-03-12 2003-09-18 Anteo Pelliconi Polyolefin masterbatch for preparing impact-resistant polyolefin articles
MY136027A (en) 2003-04-02 2008-07-31 Basell Poliolefine Spa Polyolefin masterbatch and composition suitable for injection molding
KR20060126632A (en) * 2003-11-06 2006-12-08 바셀 폴리올레핀 이탈리아 에스.알.엘 Polypropylene composition
DE602005003130T2 (en) * 2004-04-27 2008-08-14 Basell Poliolefine Italia S.R.L. Polyolefin masterbatch and composition suitable for the injection molding
CN101213249B (en) * 2005-07-01 2012-02-01 巴塞尔聚烯烃意大利有限责任公司 A propylene polymer having a broad molecular weight distribution
BRPI0615501B1 (en) 2005-07-11 2017-10-17 Basell Poliolefine Italia S.R.L Multi-layer propylene film and its preparation process
BR112012006343B1 (en) * 2009-09-22 2019-08-20 Basell Poliolefine Italia S.R.L. Propylene polymer compositions
CN102985478B (en) * 2010-07-23 2015-04-29 巴塞尔聚烯烃意大利有限责任公司 Propylene polymer compositions

Also Published As

Publication number Publication date
US9309394B2 (en) 2016-04-12
EP2411464B1 (en) 2013-05-08
US20120035327A1 (en) 2012-02-09
EP2411464A1 (en) 2012-02-01
RU2011142788A (en) 2013-04-27
KR101693062B1 (en) 2017-01-04
CN102361927B (en) 2013-10-16
JP2012521461A (en) 2012-09-13
KR20110129433A (en) 2011-12-01
WO2010108866A9 (en) 2011-03-31
CN102361927A (en) 2012-02-22
US20160272802A1 (en) 2016-09-22
BRPI1013551A2 (en) 2016-04-12
WO2010108866A1 (en) 2010-09-30
RU2531352C2 (en) 2014-10-20

Similar Documents

Publication Publication Date Title
EP1781737B1 (en) Propylene copolymer compositions with high transparency
EP1028984B1 (en) Process for preparing polypropylene
JP4233454B2 (en) Transparent and flexible propylene polymer composition
US7649052B2 (en) Impact resistant polyolefin compositions
EP2075284B1 (en) Heterophasic polypropylene with high flowability and excellent low temperature impact properties
CN100443536C (en) Polyolefin articles
US20010004657A1 (en) Olefin(co-) polymer compositions and method for producing the same andcatalyst for olefin (co-) polymerization and method for producing the same
US7482406B2 (en) Impact resistant polyolefin compositions
EP1028985B1 (en) propylene polymers and products thereof
US9145495B2 (en) Propylene polymers having broad molecular weight distribution
EP1030876B1 (en) Talc containing polypropylene compositions
US6586531B2 (en) Polyolefin masterbatch and composition suitable for injection molding
US7795352B2 (en) Polyolefinic compositions having good whitening resistance
EP2072546B1 (en) Heterophasic polypropylene with high impact properties
EP0885926B1 (en) Propylene polymer blends, processes of producing the same, and polypropylene resin compositions
KR20010015802A (en) Process for preparing polypropylene
CN101065437B (en) Elastomeric polyolefin compositions
CN100445330C (en) Polyolefin masterbatch and composition suitable for injection molding.
US9045629B2 (en) Polyolefinic compositions having good whitening resistance
US20110288213A1 (en) Multimodal polymer of propylene, composition containing the same and a process for manufacturing the same
US7348381B2 (en) High modulus, high ductility polyolefins
JP2002012734A (en) Polypropylene resin composition
CN101501129A (en) Improved high melt flow heterophasic polypropylene copolymers
JP3772648B2 (en) Polypropylene resin composition
CN102361927B (en) Polyolefin masterbatch and composition suitable for injection molding

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20130220

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A711

Effective date: 20130402

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20140709

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20140715

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20140903

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20140929

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20141028

R150 Certificate of patent (=grant) or registration of utility model

Ref document number: 5642151

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150